CN101146739A - Stabilizer and method for stabilizing hydroxylamine and stabilized hydroxylamine solution - Google Patents

Abstract

[Problem] It is the objective to provide a method of stabilizing hydroxylamine at a high temperature and a high concentration or in a case that metal impurities such as Fe got mixed with, and a stabilized hydroxylamine solution. [Means for Resolution] A method for stabilizing hydroxylamine related to the present invention is characterized by adding ethylenediamine-N,N'-di(o-hydroxyphenylacetic acid) as a preservation stabilizer.

Description

Stabilizer and method for stabilizing hydroxylamine and stabilized hydroxylamine solution

technical field

The present invention relates to stabilizers and methods for stabilizing hydroxylamine and stabilized hydroxylamine solutions.

technical background

Hydroxylamine has a wide range of industrial applications, such as intermediates for pharmaceutical raw materials and agricultural chemicals, reducing agents, metal surface treatment agents, fiber treatment and dyes. However, free hydroxylamine has extremely unstable characteristics, for example, it is easy to decompose in the presence of metal ions (especially heavy metal ions), high temperature or high concentration. Thus, relatively stable hydroxylamine salts are generally prepared and used.

However, hydroxylamine rather than the hydroxylamine salt is suitable for many applications. In addition, in many cases it is necessary to handle the aqueous solution of hydroxylamine at high temperature or high concentration. Therefore, experiments have been conducted to stabilize hydroxylamine under the conditions of high temperature, high concentration and mixing impurities such as Fe.

For example, Patent Document 1 (US Patent Publication No. 5808150) describes a stabilization method in which diethylenetriaminepentaacetic acid or triethylenetetraminehexaacetic acid is added as a stabilizer to a solution containing hydroxylamine.

However, in the hydroxylamine solution containing diethylenetriaminepentaacetic acid or triethylenetetraminehexaacetic acid as a stabilizer, there is a problem that it cannot Sufficiently inhibits the decomposition of hydroxylamine.

Patent Document 1: US Patent Publication 5808150

invention disclosure

The problem to be solved by the present invention

The object of the present invention is to provide a stabilizer and method for stabilizing hydroxylamine and a stable hydroxylamine solution.

way of solving the problem

In order to solve the above-mentioned problems, the present inventors conducted extensive and intensive research. As a result, it has been found that the addition of ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) to a hydroxylamine solution stabilizes the hydroxylamine solution, and the present invention has been accomplished. The inventors discovered the fact for the first time.

The present invention has been accomplished on the basis of the above findings and relates to the following items (1)-(3).

(1) A method for stabilizing hydroxylamine, characterized in that ethylenediamine-N,N'-di(o-hydroxyphenylacetic acid) is added to the hydroxylamine solution as a storage stabilizer.

(2) A stable hydroxylamine solution characterized by containing hydroxylamine and ethylenediamine-N,N'-di(o-hydroxyphenylacetic acid).

(3) A stabilizer for hydroxylamine, characterized in that ethylenediamine-N,N'-di(o-hydroxyphenylacetic acid) is used as an effective component.

Invention effect

The invention can stabilize the hydroxylamine solution and obtain a stable hydroxylamine solution.

Best Mode for Carrying Out the Invention

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to stabilizers for stabilizing hydroxylamine solutions, methods and stabilized hydroxylamine solutions.

The hydroxylamine stabilization involved in the present invention is a method for stabilizing hydroxylamine. In the method, ethylenediamine-N, N'-di(o-hydroxyphenylacetic acid) is added to the hydroxylamine solution as a storage stabilizer.

The present invention relates to a stable hydroxylamine solution comprising hydroxylamine and ethylenediamine-N,N'-di(o-hydroxyphenylacetic acid).

The hydroxylamine stabilizer involved in the present invention is characterized by an effective amount of ethylenediamine-N,N'-di(o-hydroxyphenylacetic acid).

By adding ethylenediamine-N, N'-bis(ortho-hydroxyphenylacetic acid) into the hydroxylamine solution, the method for stabilizing hydroxylamine involved in the present invention can inhibit the occurrence of hydroxylamine at high temperature or high concentration or when mixed with metal impurities such as Fe Case breakdown.

Although the ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) used in the method of the present invention is not particularly limited to those available on the market or industrially, it is preferred to use Impurity compounds. The reason is that the presence of impurities facilitates the decomposition of hydroxylamine in some cases. In addition, high-purity hydroxylamine with less amount of metal impurities is more suitable for electronics industry. Ethylenediamine-N,N'-di(o-hydroxyphenylacetic acid) hydrate can also be used.

The mass ratio of ethylenediamine-N, N'-bis(o-hydroxyphenylacetic acid)/hydroxylamine (ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid)/hydroxylamine) is usually 1.0×10 ^-9 to 1.0, preferably 1.0×10 ^-8 to 0.1. When the above-mentioned mass ratio is less than 1.0×10 ⁻⁹ , the effect of inhibiting the decomposition reaction of hydroxylamine cannot be obtained in some cases. In the case where the above mass ratio is greater than 1.0, it is sometimes necessary to remove excess ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid).

Regarding the method of adding ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) to hydroxylamine, ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) can be added in solid state, or can be Add after dissolving or suspending in solvent. As such solvents, water and/or organic solvents can be used. As organic solvents, mention may be made, for example, of hydrocarbons, ethers, esters and alcohols, which are capable of dissolving ethylenediamine-N,N'-di(o-hydroxyphenylacetic acid). However, the organic solvent is not limited to the above-mentioned solvents unless it has adverse effects in application. Among the above-mentioned solvents, water and/or alcohols are preferably used. Also, it can be added to the hydroxylamine solution after dissolution. Also, depending on conditions and applications, solvents can be selected from the same or different types of solutions as the hydroxylamine solution. It is preferably dissolved in the same type of solvent as the hydroxylamine solution and then added. The amount of the solvent can be appropriately selected.

Although the hydroxylamine usable in the stabilization method of the present invention is not particularly limited to those that are commercially available or industrially available, it preferably contains a small amount of metal impurities. The reason is that the presence of metallic impurities promotes the decomposition of hydroxylamine in some cases. In addition, high-purity hydroxylamine with less amount of metal impurities is more suitable for electronics industry.

In the stabilization method of the present invention, hydroxylamine may be added in a solid state, or may be added after being dissolved in a solvent. As such solvents, water and/or organic solvents can be used. As organic solvents, mention may be made, for example, of hydrocarbons, ethers, esters and alcohols. However, the organic solvent is not limited to the above-mentioned solvents unless there is an adverse effect in its use. Among the above-mentioned solvents, water and/or alcohols are preferably used.

The concentration of hydroxylamine in the hydroxylamine solution can be adjusted by proper selection of the amount of solvent. Although the concentration of hydroxylamine is not particularly limited, it is preferably within a range of 0.1 to 90% by mass, more preferably within a range of 1.0 to 70% by mass.

For example, hydroxylamine useful in the stabilization method of the present invention can be prepared by the following method. reaction process:

The method for producing hydroxylamine includes, for example, a reaction method for obtaining hydroxylamine by reacting a hydroxylamine salt with a basic compound.

As regards hydroxylamine salts, mention may be made of inorganic acid salts of hydroxylamine, such as sulfates, hydrochlorides, nitrates, phosphates, hydrobromides, sulfites, phosphates, perchlorates, carbonates and bicarbonate; and organic acid salts of hydroxylamine, such as formates, acetates and propionates, among the above, at least one kind of salts selected from the group consisting of: sulfates of hydroxylamine (NH ₂ OH·1/2 H ₂ SO ₄ ), hydrochloride (NH ₂ OH·HCl), nitrate (NH ₂ OH·HNO ₃ ) and phosphate (NH ₂ OH·1/3 H ₃ PO ₄ ).

Although parahydroxylamine salts are not particularly limited to those that are commercially available or industrially available, it is preferable to use hydroxylamine salts that contain a smaller amount of metal impurities. The reason is that the presence of metallic impurities in some cases facilitates the decomposition of the hydroxylamine salt or the resulting hydroxylamine. However, the hydroxylamine salt may contain impurities in the case where the impurities do not affect the hydroxylamine salt or decomposition of hydroxylamine and can be removed in a process such as purification or there is no problem in the use of hydroxylamine.

The hydroxylamine salt may be added in a solid state, or may be used after being dissolved or suspended in a solvent. As such solvents, water and/or organic solvents can be used. As organic solvents, mention may be made, for example, of hydrocarbons, ethers and alcohols. However, the organic solvent is not limited to the above-mentioned solvents unless there is an adverse effect in its use. Among the above solvents, solvents containing water and/or alcohol are preferably used. Furthermore, a filtrate from which insoluble salts and the like formed by the reaction have been at least partially separated can also be used as a solvent.

The amount of solvent can be appropriately selected according to the amount of hydroxylamine salt used, the reaction temperature and other conditions. Usually, the mass ratio of solvent to hydroxylamine salt (solvent/hydroxylamine salt) is 0.1-1000, preferably 1-100.

As the basic compound, at least one compound selected from the group consisting of alkali metal-containing compounds, alkaline earth metal-containing compounds, ammonia, and amines is preferred.

As regards the compounds comprising alkali metals, mention may be made of the oxides, hydroxides and carbonates of lithium, sodium, potassium, rubidium or cesium, of which the hydroxides or carbonates of sodium or potassium are preferred.

As compounds containing alkaline earth metals, mention may be made of oxides, hydroxides and carbonates of beryllium, magnesium, calcium, strontium or barium, of which oxides or hydroxides of magnesium, calcium, strontium or barium are preferred.

Ammonia can be used as a gas or as a solvent in which ammonia has been dissolved, ie in the form of an aqueous ammonia solution.

As the amine, primary, secondary or tertiary amines can be used. In addition, the amines may be monoamines or polyamines, such as diamines and triamines containing at least two amino groups in the molecule, or cyclic amines.

As monoamines, mention may be made, for example, of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, diisopropylamine, triisopropylamine , n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, diisobutylamine, triisobutylamine, sec-butylamine, di-sec-butylamine, tri-sec-butylamine, tert-butylamine, di-tert-butylamine, tri-tert-butylamine , allylamine, diallylamine, triallylamine, cyclohexylamine, dicyclohexylamine, tricyclohexylamine, n-octylamine, di-n-octylamine, tri-n-octylamine, benzylamine, dibenzylamine, tribenzylamine , diaminopropylamine, 2-ethylhexylamine, 3-(2-ethylhexyloxy)propylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-(diethylamino)propylamine, bis( 2-ethylhexyl)amine, 3-(dibutylamino)propylamine, α-phenylethylamine, β-phenylethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, Triphenylamine, o-toluidine, m-toluidine, p-toluidine, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, o-chloroaniline, m-chloroaniline, p- -Chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2,4-dinitroaniline, 2,4, 6-Trinitroaniline, p-aminobenzoic acid, sulfanilic acid, sulfonamides, monoethanolamine, diethanolamine, and triethanolamine.

As diamines, mention may be made, for example, of 1,2-diaminoethane, N,N,N',N'-tetramethyl-1,2-diaminoethane, N,N,N',N '-tetraethyl-1,2-diaminoethane, 1,3-diaminopropane, N,N,N',N'-tetramethyl-1,2-diaminopropane, N,N,N ', N'-tetraethyl-1,2-diaminopropane, 1,4-diaminobutane, N-methyl-1,4-diaminobutane, 1,2-diaminobutane, N , N, N', N'-tetramethyl-1,2-diaminobutane, 3-aminopropyldimethylamine, 1,6-diaminohexane, 3,3-diamino-N-form Dipropylamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine and benzidine.

As triamines, there may be mentioned, for example, 2,4,6-triaminophenol, 1,2,3-triaminopropane, 1,2,3-triaminobenzene, 1,2,4-triaminobenzene and 1,3,5-Triaminobenzene.

As tetraamines, mention may be made, for example, of β, β', β"-triaminotriethylamine.

As cyclic amines, mention may be made, for example, of pyrrole, pyridine, pyrimidine, pyrrolidine, piperidine, purine, imidazole, oxazole, thiazole, pyrazole, 3-pyrroline, quinoline, isoquinoline, carbazole, Piperazine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2,3-triazole, 1,2,5-triazole , 1,2,4-triazole, 1,3,4-triazole and morpholine.

Amines usable as the basic compound are not limited to the above-mentioned compounds, and may be asymmetric compounds having different types of substituents, such as ethylmethylamine. Furthermore, amines may be used alone or in combination of two or more.

Although the basic compound is not particularly limited to commercially available or industrially available compounds, compounds containing lesser amounts of metal impurities are preferred. This is the same case with hydroxylamine salts.

The equivalent ratio of the basic compound to the hydroxylamine salt (basic compound/hydroxylamine salt) is suitably in the range of 0.1-100, preferably in the range of 0.5-10, more preferably 1-2. In the case where the equivalent weight of hydroxylamine salt is 1, the equivalent weights of alkali metal, alkaline earth metal and ammonia are calculated as 1, 2 and 1, respectively. In the case of amines, the equivalent weights of monoamine and diamine are calculated as 1 and 2, respectively.

In the case where the above equivalence ratio is greater than 100, problems such as decomposition of hydroxylamine due to an excess of the basic compound arise in some cases, and it is necessary to recover many unreacted basic compounds. On the other hand, in the case where the equivalent ratio is less than 0.1, problems such as having to recover a large amount of unreacted hydroxylamine salt arise.

Basic compounds can be used after being dissolved or suspended in a solvent. As such solvents, water and/or organic solvents can be used. As organic solvents, mention may be made, for example, of hydrocarbons, ethers and alcohols. However, the organic solvent is not limited to the above-mentioned solvents unless there is an adverse effect in its application. Among the above-mentioned solvents, water and/or alcohols are preferably used. Furthermore, at least part of the filtrate from which the insoluble salts etc. formed by the reaction have been separated can also be used as a solvent.

The amount of the above-mentioned solvent can be appropriately selected according to conditions such as the amount of the basic compound used and the reaction temperature. Usually, the mass ratio of the solvent to the basic compound (solvent/basic compound) is 0.5-1000, preferably 0.8-100.

In the method for producing hydroxylamine, the reaction process, separation process, purification process, and concentration process of the reaction of hydroxylamine salt with a basic compound to obtain hydroxylamine, which will be described below, may be performed in the presence of a stabilizer. Regarding stabilizers. Known stabilizers can be used. Mention may be made, for example, of 8-hydroxyquinoline, N-hydroxyethylethylenediamine-N,N,N′-triacetic acid, glycine, ethylenediaminetetraacetic acid, cis-1,2-diaminocyclohexyl Alkane-N,N,N',N'-tetraacetic acid, trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid, N,N'-di(2-hydroxy Benzyl)ethylenediamine-N,N'-diacetic acid, N-hydroxyethyliminodiacetic acid, N,N'-dihydroxyethylaminoacetic acid, diethylenetriaminepentaacetic acid, ethylenebis (Oxyethylenenitrilo)tetraacetic acid, bis-hexamethylenetriaminepentaacetic acid, hexamethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, tris(2-aminoethyl)aminehexaacetic acid , iminodiacetic acid, polyethyleneimine, polypropyleneimine, o-aminoquinoline, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 5-chloro-1,10 -Phenanthroline, 5-phenyl-1,10-phenanthroline, hydroxyanthraquinone, 8-hydroxyquinoline-5-sulfonic acid, hydroxymethylquinoline, thioglycolic acid, mercaptopropionic acid, 1-amino- 2-Mercapto-propionic acid, 2,2-bipyridine, 4,4-dimethyl-2,2-bipyridine, ammonium thiosulfate, benzotriazole, flavonoids, Moline, quercetin, cottonseed pittin , locustine, rutin, fisetin, apigenin, galangin, coyne, flavonols, pyrophenols, anthraquinone oxide, 1,2-dioxanthraquinone, 1,4-dioxanthraquinone, 1 , 2,4-dioxanthraquinone, 1,5-dioxanthraquinone, 1,8-dioxanthraquinone, 2,3-dioxanthraquinone, 1,2,6-dioxanthraquinone, 1, 2,7-trioxanthraquinone, 1,2,5,8-tetraoxanthraquinone, 1,2,4,5,8-pentaoxanthraquinone, 1,6,8-dioxo-3-methyl -6-methoxyanthraquinone, quinalizarin, flavan, lactone, 2,3-dihydrohexono-1,4-lactone, 8-hydroxyquinaldine, 6-methyl- 8-Hydroxyquinaldine, 5,8-dihydroxyquinaldine, anthocyanin, pelargonydin, anthocyanin, delphinidin, peony anthocyanin, petunidin, mallow pigment , catechol, sodium thiosulfate, nitriloacetic acid, 2-hydroxyethyl disulfide, 1,4-dimercapto-2,3-butanediol, thiamine hydrochloride, catechol, 4 -tert-butylcatechol, 2,3-dihydroxynaphthalene, 2,3-dihydroxybenzoic acid, 2-hydroxypyridine-N-oxide, 1,2-dimethyl-3-hydroxypyridine-4- Ketone, 4-picoline-N-oxide, 6-picoline-N-oxide, 1-methyl-3-hydroxypyridin-2-one, 2-mercaptobenzothiazole, 2-mercaptocyclohexyl Thiazole, 2-mercapto-6-tert-butylcyclohexylthiazole, 2-mercapto-4,5-dimethylthiazoline, 2-mercaptothiazoline, 2-mercapto-5-tert-butylthiazoline, tetramethyl disulfide Thiuram, tetra-n-butylthiuram disulfide, N, N'-diethylthiuram disulfide, tetraphenylthiuram disulfide, thiuram disulfide, thiourea, N, N' -Diphenylthiourea, di-o-tolylthiourea, ethylenethiourea, thioacetamide, 2-thiouracil, thiocyanuric acid, thioformamide, thioacetamide, sulfur Propionamide, thiobenzamide, thionicotinamide, thioacetophenone, thiobenzanilide, 1,3-dimethylthiourea, 1,3-diethyl-2-thiourea, 1 -Phenyl-2-thiosemicarbazide, 1,3-diphenyl-2-thiourea, thiocarbamide, thiosemicarbazide, 4,4-dimethyl-3-thiosemicarbazide, 2-mercaptoimidazoline , 2-thiohydantoylurea, 3-thioxo-1,2,4-triazole (thiourazole), 2-thioaminomalonylurea, 4-thioaminomalonylurea, thiopentyl Alcohol, 2-thiobarbituric acid, thiocyanuric acid, 2-mercaptoquinoline, thiocoumazone, thiocumothiazone, thiosaccharin, 2-mercapto Benzimidazole, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, trimethylphosphine, triethylphosphine, and triphenylphosphine. In addition, ethylenediamine-N,N???-bis(o-hydroxyphenylacetic acid) can also be used as a stabilizer.

The above stabilizers may be used alone or in combination of two or more. The addition of stabilizers can inhibit the decomposition of hydroxylamine and hydroxylamine salts caused by metal impurities.

Although the stabilizer is not particularly limited to those available on the market or industrially, it is preferable to use a stabilizer containing a smaller amount of metal impurities. This situation is the same as that of hydroxylamine salt.

The mass ratio of the stabilizer to the hydroxylamine salt (stabilizer/hydroxylamine salt) is suitably in the range of 1.0×10 ⁻⁹ to 1.0, preferably in the range of 1.0×10 ⁻⁸ to 0.1. In the case where the above mass ratio is less than 1.0×10 ⁻⁹ , suppression of the decomposition reaction of hydroxylamine or hydroxylamine salt due to metal impurities cannot sometimes be obtained. In the case where the above mass ratio is greater than 1.0, it is sometimes necessary to remove or recover the excess stabilizer.

The stabilizer may be used in a solid state, or may be used after being dissolved or suspended in a solvent. As such solvents, water and/or organic solvents can be used. As organic solvents, mention may be made, for example, of hydrocarbons, ethers, esters and alcohols. However, the organic solvent is not limited to the above-mentioned solvents unless there is an adverse effect in its application. Among the above-mentioned solvents, water and/or alcohols are preferably used. The amount of the solvent can be appropriately selected according to conditions such as the kind and amount of the stabilizer used and the reaction temperature.

A preferred reaction scheme in the process for the preparation of hydroxylamine is as follows. During the reaction, the hydroxylamine salt is added to and reacted with the reaction solution in which the basic compound has been dissolved or suspended in the solvent. As described above, by using the method of adding a hydroxylamine salt to a reaction solution containing a basic compound, it is difficult for the formed hydroxylamine to form a complex with the by-product salt, and it is difficult to absorb or mix the by-product insoluble salt.

Also, in the case of adding a hydroxylamine salt to a reaction solution containing a basic compound, it is preferably added while maintaining the pH of the reaction liquid at preferably 7 or higher, more preferably 7.5 or higher, further preferably 8 or higher Hydroxylamine salt. By keeping the pH of the reaction solution in the above range, the obtained hydroxylamine is less likely to form a complex with the by-product salt, and is less likely to absorb or mix the by-product insoluble salt.

However, during the reaction, a basic compound may be added to and reacted with the reaction solution in which the hydroxylamine salt has been dissolved or suspended.

Furthermore, in the method for producing hydroxylamine, the reaction process may also be a reaction process in which a hydroxylamine salt and a basic compound are simultaneously supplied and reacted. In this case, it is preferable to adjust the addition amounts of the hydroxylamine salt and the basic compound while maintaining the pH of the reaction solution at preferably 7 or higher, more preferably 7.5 or higher, further preferably 8 or higher. The hydroxylamine salt and the basic compound can be added in the solid state, or after being dissolved or suspended in a solvent. Also, in the case where the basic compound is ammonia or the like, gas may be introduced.

During the reaction for preparing hydroxylamine, there is no particular limitation on the method of adding the stabilizer, and known methods can be used. For example, a stabilizer can be introduced into the reactor before the reaction starts, or, if necessary, can be added during the reaction. Also, the stabilizer, together with the basic compound and the hydroxylamine salt, may be added after being dissolved or suspended in the solvent.

During the above reaction process, the reaction temperature is preferably 0-80°C, more preferably 5-50°C. In the case where the reaction temperature is higher than 80°C, problems such as decomposition of hydroxylamine may occur. On the other hand, in the case where the reaction temperature is lower than 0°C, the reaction rate decreases and there may be a problem of decreased productivity.

The reaction temperature can be kept in a constant range by removing the heat of reaction, which is generated by the reaction of hydroxylamine salt and basic compound, out of the system by using water, hot water or heating medium. Also, the heat exhausted to the outside of the system using water, hot water or heating medium can be preferably used as a heat source for other equipment.

The reaction process in the production method of hydroxylamine can be carried out by known methods such as batch system, semi-batch system and continuous system.

Separation process:

The process for preparing hydroxylamine may include, for example, a process of separating hydroxylamine and insoluble material

The insoluble material is, for example, an insoluble material deposited in the reaction solution during the above reaction.

As the insoluble material, there may be mentioned a salt formed by reacting a hydroxylamine salt with a basic compound during the above reaction, a hydroxylamine salt, a basic compound, and the like.

More specifically, when the solubility reaches above the limit, in the case where the salt formed by the reaction of the hydroxylamine salt with the basic compound, the hydroxylamine salt, the basic compound, etc. are deposited as insoluble salts during the above reaction, the separation of the insoluble material may be included. separation process.

As for the separation method, known methods such as filtration, compression, centrifugation, sedimentation and flotation can be used. For example, for separation by filtration, any of natural filtration, pressurized filtration, and reduced-pressure filtration may be performed. For separation by sedimentation, clarification separation and sedimentation concentration can be performed. For separation by flotation, pressurized flotation or ionized flotation can be performed.

Hydroxylamine that adheres or has been mixed into the insoluble material can be recovered by washing the insoluble material separated during the separation process.

As for the solvent used for washing the insoluble material, the solvent used during the reaction can be used, and another solvent can also be used. As a solvent for washing, water and/or an organic solvent can be used. As the organic solvent, there may be mentioned, for example, hydrocarbons, ethers, esters, alcohols and the like. However, the organic solvent is not limited to the above solvents, and any organic solvent can be used as long as it has no adverse effect on the recovery of hydroxylamine. Among the above solvents, water and/or alcohol are preferably used as solvents for washing. The amount of solvent used for washing can be appropriately selected according to the kind, amount and separation conditions of the insoluble material.

In the case where insoluble materials are separated in the above separation process, the temperature is preferably 0-80°C, more preferably 5-50°C. If the temperature is higher than 80°C, problems such as decomposition of hydroxylamine may occur. On the other hand, in the case where the temperature of the reaction solution is lower than 0° C., there may arise a problem that energy required for cooling increases. Part or all of the filtrate from which the insoluble material has been separated and/or the filtrate from which the insoluble material has been washed in the above separation process can be used as a solvent for dissolving or suspending the reaction raw material hydroxylamine salt and/or basic compound.

Similar to the reaction process, the above separation process is preferably carried out in the presence of a stabilizer for hydroxylamine. During isolation, new stabilizers can be added, or stabilizers already used in previous processes can be used. For the above-mentioned stabilizer, the stabilizer that is the same as or different from the stabilizer used in the reaction process can be selected according to the conditions and applications. By adding a stabilizer, side reactions such as decomposition of hydroxylamine due to metal impurities can be suppressed, and production efficiency of hydroxylamine can be improved.

The stabilizer is suitably used in an amount such that the mass ratio of stabilizer to hydroxylamine (stabilizer/hydroxylamine) is in the range of 1.0×10 ⁻⁹ to 1.0, preferably in the range of 1.0×10 ⁻⁸ to 0.1. When the above-mentioned mass ratio is less than 1.0×10 ⁻⁹ , the decomposition reaction of hydroxylamine due to metal impurities cannot be suppressed in some cases. In the case where the above mass ratio is greater than 1.0, it is sometimes necessary to remove or recover the excess stabilizer.

The separation process in the production method of hydroxylamine can be performed by known methods such as batch system, semi-batch system and continuous system.

Purification process:

A method for preparing hydroxylamine includes a process of purifying the hydroxylamine solution obtained above, for example, by ion exchange.

The method of ion exchange can be performed by known methods such as cation exchange, anion exchange and chelate exchange.

Purification by cation exchange can be performed by a known method using a strongly acidic cation exchange resin, a weakly acidic cation exchange resin, or the like. It is preferable to acid-treat the cation exchange resin in advance to make the cation exchange resin H-form before use.

Purification by anion exchange can be performed by a known method using strongly basic anion exchange resins, weakly basic anion exchange resins, and the like. It is preferable to subject the anion exchange resin to alkali treatment in advance so that the anion exchange resin is in the OH form before use.

Purification by chelate exchange can be performed by a known method using a chelate exchange resin or the like. It is preferred to acid-treat the chelate exchange resin in advance so that the chelate exchange resin is in H form before use.

The purification can be performed by combining cation exchange, anion exchange and chelation exchange. For example, anion exchange can be performed after cation exchange, or cation exchange can be performed after anion exchange. In addition, single bed resins, or mixed bed resins in which cation exchange resins and anion exchange resins have been mixed can also be used.

The temperature during the ion exchange is preferably 0-70°C, more preferably 5-50°C. In the case where the ion exchange temperature is higher than 70° C., a problem of decomposition of hydroxylamine may occur. On the other hand, in the case where the ion exchange temperature is lower than 0° C., there may be a problem that energy required for cooling increases.

Part of the hydroxylamine solution obtained in the above purification process can be used as a solvent for dissolving or suspending the reaction raw materials hydroxylamine salt and basic compound.

Similar to the reaction process, the above purification process is preferably carried out in the presence of a stabilizer for hydroxylamine. During purification, new stabilizers can be added, or stabilizers already used in previous processes can also be used.

For the above-mentioned stabilizer, the stabilizer that is the same as or different from the stabilizer used in the reaction process can be selected according to the conditions and applications. By adding a stabilizer, side reactions such as the decomposition of hydroxylamine due to metal impurities can be suppressed, and the purification efficiency of hydroxylamine can be improved.

The stabilizer is suitably used in an amount such that the mass ratio of stabilizer to hydroxylamine (stabilizer/hydroxylamine) is in the range of 1.0×10 ⁻⁹ to 1.0, preferably in the range of 1.0×10 ⁻⁸ to 0.1. When the above-mentioned mass ratio is less than 1.0×10 ⁻⁹ , the decomposition reaction of hydroxylamine due to metal impurities cannot be suppressed in some cases. In the case where the above mass ratio is greater than 1.0, it is sometimes necessary to remove or recover the excess stabilizer.

In the production method of hydroxylamine, the purification process by ion exchange can be performed by known methods such as batch system, semi-batch system and continuous system.

Concentration process

The process for producing hydroxylamine includes, for example, a process of concentrating hydroxylamine by distillation in the bottom section of the column.

The distillation method can be performed by known methods such as simple distillation, multi-stage distillation, steam distillation and flash distillation.

For example, a hydroxylamine solution with a high concentration of hydroxylamine can be obtained from the bottom section by simple distillation or multistage distillation.

As for the distillation column, an ordinary tray column such as a bubble column and a screen column may be used, or an ordinary packing such as a Raschig ring, a pearl ring, and a saddle support may be assembled.

The distillation temperature is preferably a temperature in the column bottom section of 0-70°C, more preferably 5-60°C. In the case of temperatures above 70° C. in the bottom section, problems of decomposition of hydroxylamine may arise. On the other hand, in the case where the bottom temperature of the column is lower than 0°C, there may arise a problem that a large amount of energy is required for cooling.

The pressure of the distillation is determined according to the relationship with the temperature, and the pressure in the column bottom section is preferably 0.5-60kPa, more preferably 0.8-40kPa.

Part of the hydroxylamine solution obtained in the above-mentioned concentration process can be used as a solvent for dissolving or suspending the reaction raw materials hydroxylamine salt and basic compound.

In some cases, a solution with a low concentration of hydroxylamine can be obtained from the top or side of the distillation column. All or part of the obtained hydroxylamine solution can be used as a solvent for dissolving or suspending the reaction raw materials hydroxylamine salt and basic compound.

Similar to the reaction process, the concentration process is preferably carried out in the presence of a stabilizer of hydroxylamine. During concentration, new stabilizers can be added, or also stabilizers already used in previous processes can be used.

For the above-mentioned stabilizer, the stabilizer that is the same as or different from the stabilizer used in the reaction process can be selected according to the conditions and applications. By adding a stabilizer, side reactions such as decomposition of hydroxylamine due to metal impurities can be suppressed, and production efficiency of hydroxylamine can be improved.

The stabilizer is suitably used in an amount such that the mass ratio of stabilizer to hydroxylamine (stabilizer/hydroxylamine) is in the range of 1.0×10 ⁻⁹ to 1.0, preferably in the range of 1.0×10 ⁻⁸ to 0.1. When the above-mentioned mass ratio is less than 1.0×10 ⁻⁹ , the decomposition reaction of hydroxylamine due to metal impurities cannot be suppressed in some cases. In the case where the above mass ratio is greater than 1.0, it is sometimes necessary to remove or recover the excess stabilizer.

In the production method of hydroxylamine, the concentration process of concentrating hydroxylamine by distillation in the bottom section of the column can be performed by known means, such as a batch system, a semi-batch system and a continuous system.

Also, the method for preparing hydroxylamine may include a process of purifying hydroxylamine obtained in the above-mentioned concentration process by ion exchange.

The method of ion exchange can be performed by known methods such as cation exchange, anion exchange and chelate exchange.

Purification by cation exchange can be performed by a known method using a strongly acidic cation exchange resin, a weakly acidic cation exchange resin, or the like. It is preferable to acid-treat the cation exchange resin in advance to make the cation exchange resin H-form before use.

Purification by anion exchange can be performed by a known method using strongly basic anion exchange resins, weakly basic anion exchange resins, and the like. It is preferable to subject the anion exchange resin to alkali treatment in advance so that the anion exchange resin is in the OH form before use.

Purification by chelate exchange can be performed by a known method using a chelate exchange resin or the like. It is preferred to acid-treat the chelate exchange resin in advance so that the chelate exchange resin is in H form before use.

The purification can be performed by a combination of cation exchange, anion exchange and chelation exchange. For example, anion exchange can be performed after cation exchange, or anion exchange can be followed by cation exchange.

Furthermore, a single bed resin, or a mixed bed resin in which a cation exchange resin and an anion exchange resin are mixed may also be used.

The temperature during the ion exchange is preferably 0-70°C, more preferably 5-50°C. In the case where the ion exchange temperature is higher than 70° C., a problem of decomposition of hydroxylamine may occur. On the other hand, in the case where the ion exchange temperature is lower than 0° C., there may be a problem that energy required for cooling increases.

Part of the hydroxylamine solution obtained in the above purification process can be used as a solvent for dissolving or suspending the reaction raw materials hydroxylamine salt and basic compound.

Similar to the reaction process, the above purification process is preferably carried out in the presence of a stabilizer for hydroxylamine. During purification, new stabilizers can be added, or stabilizers already used in previous processes can also be used.

For the above-mentioned stabilizer, the stabilizer that is the same as or different from the stabilizer used in the reaction process can be selected according to the conditions and applications. By adding a stabilizer, side reactions such as decomposition of hydroxylamine due to metal impurities can be suppressed, and production efficiency of hydroxylamine can be improved.

The stabilizer is suitably used in an amount such that the mass ratio of stabilizer to hydroxylamine (stabilizer/hydroxylamine) is in the range of 1.0×10 ⁻⁹ to 1.0, preferably in the range of 1.0×10 ⁻⁸ to 0.1. When the above-mentioned mass ratio is less than 1.0×10 ⁻⁹ , the decomposition reaction of hydroxylamine due to metal impurities cannot be suppressed in some cases. In the case where the above mass ratio is greater than 1.0, it is sometimes necessary to remove or recover the excess stabilizer.

As mentioned above, methods for the preparation of hydroxylamine that can be used in the stabilization method of the present invention include, for example:

(1) reaction process of hydroxylamine salt and basic compound to obtain hydroxylamine,

(2) the process of separating hydroxylamine and insoluble material,

(3) Purification process of purifying hydroxylamine by ion exchange,

(4) Concentration process in which hydroxylamine is concentrated in the column bottom section by distillation.

The above method is preferably carried out in the order of reaction process, separation process, purification process and concentration process. Also, after performing the above-mentioned process (1), the processes (2)-(4) may be performed in any order. Also, the same process can be performed two or more times.

For example, the concentration of hydroxylamine that can be obtained by the above method is 10% by mass or higher. Also, hydroxylamine at a concentration of 20% by mass or higher can be obtained. In addition, hydroxylamine at a concentration of 40% by mass or higher can also be obtained.

For the hydroxylamine obtainable by the above method, the content of various metals that may be contained as impurities is, for example, 1 mass ppm or less. Furthermore, hydroxylamine having a content of various metals of 0.1 mass ppm or less can also be obtained. Further, hydroxylamine having a content of various metals of 0.01 mass ppm or less can also be obtained. As metals, mention may be made of alkali metals and alkaline earth metals derived from the basic compounds used during the reaction, and Fe which significantly promotes the decomposition of hydroxylamine.

Regarding the hydroxylamine obtainable by the above method, the content of various anions that may be contained as impurities is, for example, 100 mass ppm or less. Moreover, various hydroxylamines having an anion content of 10 mass ppm or less can also be obtained. Further, various hydroxylamines having an anion content of 1 mass ppm or less can also be obtained. As anions, there may be mentioned sulfate ions, chloride ions, nitrate ions and the like derived from the raw material hydroxylamine salt.

In the case where ethylenediamine-N, N'-bis(o-hydroxyphenylacetic acid) is used in any of the above processes (1)-(4), ethylenediamine-N, N'-bis(o-hydroxyphenylacetic acid) Hydroxyphenylacetic acid) does not need to be removed or recovered, and can also be used as a storage stabilizer. In this case, the determined amount of ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) added as a storage stabilizer includes the pre-existing ethylenediamine-N,N' in solution - the amount of di(o-hydroxyphenylacetic acid).

Implementation

The present invention will be described in detail below using embodiments and comparative examples. However, the present invention is not limited to these embodiments.

(Embodiments 1 and 2)

Ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) was added in such a way that a 50% by mass hydroxylamine aqueous solution contained ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) at a predetermined concentration Added as a storage stabilizer to a 50% by mass aqueous solution of hydroxylamine having an Fe concentration of 0.01 mass ppm or less.

100 g of the above-mentioned 50% by mass hydroxylamine aqueous solution was charged into a 500 ml container made of PFA with a cover, and the container was placed in a 60° C. thermostatic chamber after fixing the cover.

After 30 days, the color of the aqueous hydroxylamine solution was determined visually. The concentration of hydroxylamine was then measured by hydrochloric acid titration, and the decomposition rate of hydroxylamine was obtained by the following expression.

Hydroxylamine decomposition rate (%)=(50-A)/50×100

A=hydroxylamine concentration (mass %) after 30 days.

The results are listed in Table 1.

(comparative examples 1-3)

The carrying out mode of comparative example 1-3 is similar to embodiment 1 and 2, but adds the storage stabilizer listed in table 1 to replace ethylenediamine-N, N'-two (ortho-hydroxyphenylacetic acid) as storage stabilizer agent.

The results are listed in Table 1.

Table 1 Implementation storage stabilizer Concentration of preservation stabilizer (mass ppm) Decomposition rate of hydroxylamine (%) 1 Ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) 300 54 2 Ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) 500 6.1 Comparative example 1 none 0 12 Comparative example 2 Diethylenetriaminepentaacetic acid 300 7.7 Comparative example 3 Triethylenetetraminehexaacetic acid 300 10

(Embodiments 3 and 4)

Ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) was added in such a way that a 50% by mass hydroxylamine aqueous solution contained ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) at a predetermined concentration Added as a storage stabilizer to a 50% by mass aqueous hydroxylamine solution having an Fe concentration of 0.01 mass ppm or less.

20 g of the above-mentioned 50% by mass hydroxylamine aqueous solution was put into a 500 ml PFA container with a lid.

The 1000 mg/L standard solution of Fe(III) was added to 50% by mass hydroxylamine aqueous solution in such a way that the Fe content reached a specific concentration. The container was then placed in a constant temperature room at 50° C. after fixing the lid.

After 7 days, the hydroxylamine concentration was measured by hydrochloric acid titration, and the decomposition rate of hydroxylamine was obtained by the following expression.

Hydroxylamine decomposition rate (%)=(50-B)/50×100

B=hydroxylamine concentration (mass %) after 7 days.

The results are listed in Table 2.

(comparative examples 4-6)

The carrying out mode of comparative example 4-6 is similar to embodiment 3 and 4, but adds the storage stabilizer listed in table 2 to replace ethylenediamine-N, N'-two (ortho-hydroxyphenylacetic acid) as storage stable agent.

Table 2 Implementation storage stabilizer Concentration of preservation stabilizer (mass ppm) Fe(III) concentration (mass ppm) Decomposition rate of hydroxylamine (%) 3 Ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) 300 1.0 1.1 4 Ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) 500 1.0 0.45 Comparative example 4 none 0 10 100 Comparative example 5 Diethylenetriaminepentaacetic acid 300 10 70 Comparative example 6 Triethylenetetraminehexaacetic acid 300 10 91

Through the above embodiments and comparative examples, it can be found that ethylenediamine-N,N'-bis(o-hydroxyphenylacetic acid) as a storage stabilizer can effectively stabilize the aqueous solution of hydroxylamine in the presence of Fe.

Industrial applicability

By the present invention, the hydroxylamine solution is stabilized and a stabilized hydroxylamine solution can be obtained. In particular, through the present invention, the stability of hydroxylamine at high temperature, high concentration and the presence of metal impurities is significantly improved, and the application range of hydroxylamine in many applications is expanded.

Claims (3)

1. the method for a stabilizing hydroxylamine comprises quadrol-N, and N '-two (neighbour-hydroxyphenyl acetic acid) adds the step of hydroxylamine solution as preserving stabilizer.

2. stabilized hydroxylamine solutions, it comprises azanol and quadrol-N, N '-two (neighbour-hydroxyphenyl acetic acid).

3. the stablizer of an azanol, quadrol-N wherein, N '-two (neighbour-hydroxyphenyl acetic acid) is an active principle.